Treatment oe textile and other materials



Patented Mar. 7, 1933 UNITED STATES PATENT OFFICE GEORGE HOLLAND ELLIS,HENRY CHARLES OIIPIN, AND RALPH CHARLES STOREY, OI

BPONDON, NEAR DERBY, ENGLAND, ASSIGNORS TO CELANESE CORPORATION 01'AMERICA, A CORPORATION OF DELAWARE TREATMENT OI TEXTILE AND OTHERMATERIALS No Drawing. Application filed June 7, 1930, Serial No.459,828, and in Great Britain July 4, 1929.

This invention relates to the colouration by dyeing, printing,stencilling or otherwise of textile or other materials.

Vat colouring matters have long been employed on a very extensive scalefor the colouration of cellulosic materials. The colouring matters havebeen applied to the sand materials in the form of alkali salts of theirreduction products, the so-called leuco compounds, and the colourationsobtained have been highly valued on account of them resistance to theagencies to which textlle materials are commonly subjected. Theappllcation of these vat colouring matters to other textile materialshas in the past met wlth very serious difficulties owing either to thecomparatively small afiinity of the materials for the alkali salts ofthe leuco compounds, or to their being easily injured by the alkalineconditions existing in the dye vats. The application of the vatcolouring matters to WOOl and silk, for instance, has in thepast beenprincipally confined to the use of a few colouring matters which can bevatted in the presence'of small quantities of alkali.

The very remarkable discovery has been made that the free leucocompounds of vat colouring matters have good affinity for and can bedirectly applied to very many textile and other materials to producevaluable colourations thereon.

According to the present invention therefore, the colouration of textileor other materials made of or containing cellulose acetate or otherorganic derivatives of cellulose is effected by processes comprising theapplication of free leuco compounds of vat colouring matters. Vatcolouring matters may thus be applied to the material in the absence ofalkali, for example under neutral or acid conditions, a very greatadvantage in the treatment of cellulose ester materials. Moreover theafiinities in relation to any particular fibre, of the leuco compoundsof vat dyestuffs uncombined with alkalies in general differ considerablyfrom those of the compounds of leuco bodies with alkalies. Inconsequence the invention renders possible the production ofcolourations, for example colourations on materials comprising two ormore types of fibre, which are difiicult or impossible of attainment byhitherto known methods.

Free leuco compounds of the vat colouring matters may be applied to thetextile or other materials in any convenient manner, for example in theform of solutions, e. g. in organic solvents. They are however mostsatisfactorily and conveniently applied in the form of aqueousdispersions or suspensions, and this method of application constitutes avery important feature of the present invention. Contrary toexpectation, it has been found that the solutions, dispersions, or otherpreparations containing the free leuco compounds are remarkably stablein the presence of air. Cellulose ester or ether materials show anexceptionally good affinity for the free leuco compounds, often greaterthan the aflinity of the same materials for the alkali salts of theleuco compounds. For instance the free leuco compounds of the indigoidcolouring matters have such remarkably good aflinity for cellulose estermaterials under neutral or acid conditions that it is even possible torinse the materials before oxidizing the leuco compound, andcolourations of excellent fastness to rubbing are thereupon obtained. Inaddition, as the dyeing operation can be effected under non-alkalineconditions, all danger of saponification of the cellulose ester may beavoided. A further valuable feature of the invention resides in the factthat the range of conditions for optimum dyeing is in general much widerthan with alkaline vats. Thus, not only does the invention enablecolouring to be effected under much less closely controlled conditions,but it much facilitates the application of mixtures of dye- Vatdyestuffs of any desired kind may be employed for application accordingto the process of the present invention, and the term Vat dyestuff is tobe understood as comprising not only those colouring matters commonlyemployed for application to textile materials. from alkaline vats, butany other colouring matters capable of yielding by reduction compoundswhich may be converted by oxidation into the original colouring matters.The following are given as instances of such colouring matters orclasses of colouring matters 1. Indi 0 and allied colouring matters.

(a) In igo and its derivatives, for example N .N'-dimethyl indigo andhalogenated indigoes, e. g. Ciba blue 2B (Colour Index 1184 (b)Halogenated indirubines, e. g. Ciba heliotrope B (Colour Index 1205).

(c) Thioindigo and its derivatives, for instance halogenatedthioindigoid dyes, e. g Ciba Bordeaux B (Colour Index 1208).

(d) Dinaphthindigoid dyes, e. g. Ciba green G (Colour Index 1198).

(e) Indigoid dyes obtainable by condensing isatins or thioisatins withu-oxynaphthalenes or woxy-anthracenes or derivatives thereof and ifdesired subsequently halogenating, e. g. Alizarin indigo 3R (ColourIndex 1200) and Helindone blue 3GN (Colour Index 1203).

2. Anthraquinone colouring matters.

(a) Simple amino-derivatives, e. g. l-hydroxyl-amino-anthraquinone; 1:5-diamino- 4 8-dihydroxy-anthraquinone; l-methylamino-anthraquinone; 1 4dianilide-anthraquinone.

(b) Anthraquinone-quinolines, e. g. 1:2-dihydroxy-anthraquinone-quinoline (Colour Index 1066).

(c) Acylamino anthraquinones, e. g. l-acetylamino-anthraquinone; 1t-dipropionylaminoanthraquinone 1 :5 dibenzoylaminoanthraquinone (ColourIndex 1132); succinyl-alphaamino anthraquinone (Colour Index 1139) 1:5-dibenzoylamino-4 8-dihydrox -anthraquinone (Colour Index 1134).

(d Anthrapyridones, e. g. 4-methylaminoanthrapyridone.

(e) Anthraquinone-mercaptans including their derivatives substituted inthe nucleus and/or the mercapto groups.

(f) Benzanthrones and dibenzanthrones, e. g. Violanthrone (Colour Index1099); Iso-violanthrone (Colour Index 1103) Amino-violanthrone (ColourIndex 1102); Dimgthoxy-dibenzanthrone (Colour Index 1101 (g) Pyranthroneand its derivatives.

(h) Anthraflavone (Colour Index 1095).

(i) Anthraquinone acridones, e. g. anthraquinone 1 (NI-I) -2 (CO)-naphthacridone (Colour Index 1162).

(j) Dianthraquinonyls and acidylamino derivatives.

Dianthraquinonylamines and derivatives, e. g. acidylamino derivatives.

(Z) Anthraquinone azines and hydroazines, e. g.dianthraquinone-dihydroazines and their halogenated derivatives such as1 2.1 2'-dianthraquinone azine (Colour Index 1106) and its dichlorderivatives (Colour Index 1113).

(m) Anthraquinone oxazines. (n) Anthraquinone dioxides.

0) Anthraquinone thiazines.

p) Anthraquinone disulphides. (g) Anthraquinone xanthones. (1-)Anthraquinone thioxanthones. (a) Anthraquinone carbazoles.

t Anthraquinone thiazoles.

3. Derivatives of benzoquinone and naphthoquinones, e. g. thosementioned in United States patent applications S. Nos. 379,874 and379,87 5 both filed 20th July, 1929.

4. Indophenols and their derivatives, e. g. halogen derivatives.

5. Perylene quinones and their amino, halogen and other derivatives.

6. Dyestuffs obtainable by alkali fusion of imides and substitutedimides of naphthalene peridicarboxylic acids and the dyestuffsobtainable by condensing naphthalene 1: 1: 5 S-tetraearboxylic acidswith monoor diamines.

7. Sulphur dyestufi's including not only those colouring matterscommonly applied from sulphide baths but also those sulphur colouringmatters commonly applied to cellulosic materials from hydrosulphite orother vats, for example the colouring matters obtained by sulphurizingindophenols derived from. carbazol (see Colour Index Nos. 969, 970, 971,etc.)

Dispersions or suspensions of free leuco compounds of colouring mattersmay be obtained by any convenient means, whether mechanical orotherwise. For example the free leuco compounds themselves may bedirectly converted into aqueous dispersions by mechanical treatment orby treatment with dispersing agents and/or protective colloids.Alternatively the leuco compounds may be liberated or formed in thepresence of dispersing agents and/or protective colloids, and in thismanner dispersions or suspensions directly applicable for dyeing may beproduced. For example vat colouring matters may be vatted with the aidof alkali and bydrosulphite or other reducing agents in the known mannerand acidified with a suitable organic or inorganic acid in presence ofprotective colloids and/or dispersing agents. Moreover, the protectivecolloids or dispersing agents themselves may be converted by theacidification into other and even more suitable forms. The dispersingagents and protective colloids should be as stable as possible under theconditions in which the dispersions or supensions are to be stored orapplied. As examples of dispersing agents or protective colloids thefollowing may be in stanced:-

Sulphoaromatic fatty acid compounds, e. g. sulphobenzene palmitic acidcompounds (see United States Patent No. 1,694,413).

Sulphoaromatic ricinoleic acid compounds, e. g.sulphonaphthalenericinoleic acid, (see United States patent applicationS. No. 134,138 filed 7th September, 1926) Naphthenic acids or othercarbocyclic compounds containing salt-forming groups or salts of suchacids or compounds (see United States Patent No. 1,618,414).

Sulphonated oil compounds, e. g. sul-- phonated castor oil.

.Furfural-naphthalene sulphonic acid compounds (see United States patentapplication S. No. 390,423 filed 4th September, 1929).

Resino-naphthalene sulphonic acid compounds (see United States patentapplication S. No. 390,424 filed 4th September, 1929).

Formaldehyde naphthalene sulphonic acld compounds.

Alkyl-, cycloalkyl-, and aralkyl-naphthalene sulphonic acids.

Sulphite cellulose waste liquor or 1ts constituents or products oftransformation, e. g. lignin sulphonic acid compounds.

Sulphonic acid compounds of mineral oils, tar oils, brown coal tar oils,and the like, and their products of condensation with alcohols.

Sulphonic acid compounds of distillation residues of benzaldehyde.

Molasses.

Carbohydrates including gums.

Glue and gclatine.

Aqueous dispersions or suspensions of the free leuco compounds may beacid, neutral or even slightly alkaline. For examplethey may havehydrogen ion concentrations corresponding to pH values lying between 3and 9, for instance between 4 and 8. In general, the colouration ofcellulose acetate and other organic substitution derivatives ofcellulose may be accomplished in a highly satisfactory manner withaqueous suspensions or dispersions containing sufficient acetic, formic,or other organic acid to render them slightly acid to litmus.

' The dispersions of the free leuco compounds may be prepared in thedyebaths themselves, 'or in the form of more or less concentratedliquid, paste, solid, or powdered or other preparations which may beused for the preparation of dyebaths. Such preparations may be obtainedfor instance by removal of water by evaporation or otherwise from lessconcentrated dispersions, or by acidifying concentrated solutions ofalkali salts of leuco compounds of vat colouring matters in the presenceof dispersing agents and/or protective colloids, or by simple grindingof the leuco compounds with dispersing agents and/or protective colloidswith or without water. The preparations preferably contain water and mayreceive additions of agents, e. g. reducing agents or acids, adapted toin crease their stability in the presence of air. These preparationscomprise an important feature of the present invention, which furtherincludes preparations which contain dispersing agents, particularlythose referred to above, and/or protective colloids, together with anycompounds, e. g. the alkali salts of and/or dispersing agents, and afteradjusting the acidity if necessary for the purpose in view.

The solutions or dispersions of free leuco compounds maybe applied totextile or other materials in any convenientmanner, for ex- ,ample bydyeing, padding printing, stencilling or the like. Aqueous dispersionsor suspensions are preferably employed under neutral or acid conditions.If desired or requisite they may receive additions of thickening agents,for example when they are to be applied by padding or printing.Solutions or suspensions of free leuco compounds used ac cording to theinvention appear to be in gen eral mu:h more stable than the alkalinevats hitherto employed and in consequence manipulation of the materialsis in manycases much facilitated. For example it is even possible to dyefabrics on winch machines or in open width on jigger machines, where inboth cases there is a considerable passage of air through the material.

If desired the free leuco compounds of vat dyestuffs may be applied inconjunction with swelling agents for the materials to be colcured,

The oxidation of the leuco compounds on the materials may be effected byany suitable means, for example by simple air oxidation, treatment withbichromate and acid, treatment with bleaching powder, or treatment withsoap and sodium perborate, and very satisfactory results have beenobtained by oxidation in a bath containing soap and hydrogen peroxide,particularly as regards evenness of shade and little tendency of theresulting dyeings to rub.

The new process of colouration is applicable to any materials consistingof or containing cellulose esters or ethers and is particular- 1yvaluable in the colouration of su h textile and other materials as areliable to injury by alkali, for example materials made of or containingcellulose esters, for example filaments, yarns, fabrics, ribbons andfilms made of these esters, e. g. cellulose acetate, formate,propionate. or butyrate, or the products obtained by the treatment ofalkalized cellulose with esterifying agents, for instance the productknown as immunized cotton obtained with p-toluene sulpho chloride. Theinvention is also applicable to the colouration of other organicsubstitution derivatives of cellulose for example cellulose ethers, e.g. methyl, ethyl, or benzyl cellulose, or the condensation products ofcellulose and glycols or other polyhydric alcohols. Particularlysatisfactory colourat-ions may for instance be produced on organicderivatives of cellulose in accordance with the invention by means ofthe free leuco compounds of indigoid and thioindigoid colouring mattersand colouring matters containing a single ant-hraquinone nucleus, forexample of the following series :anthraquinone acridones, oxazines,dioxides, thiazines, disulphides, xanthones, thioxanthones, carbazoles,and thiazoles. The importance of the invention will be appreciated inView of the low affinity or lack of affinity exhibited by celluloseacetate or other organic derivatives of cellulose for the alkalicompounds of leuco anthraquinone vat dyestuffs.

Mixed materials containing two or more kinds of textile fibres may bedyed by the process of the invention, the various fibres being colouredin solid or contrasting shades according to their relative afiinitiesfor the colouring matter or matters; thus solid shades can be obtainedon mixtures of cellulose acetate with wool or natural silk.

Cellulosic materials, for example cotton, linen, or the regeneratedcelulose type of artificial silk show in general little or no affinityfor the free leuco compounds of vat colouring matters applied inaccordance with the present invention. The new process therefore renderspossible the production of valuable cross-dyed effects on certain mixedmaterials. for example on fabrics composed of cellulose acetate andcotton, or natural silk and cotton, or cel'ulose acetate and aregenerated cellnlosic type of artificial silk. For example thecellulose acetate in such a mixed material may be dyed with a dispersionof the free leuco compound of a vat colouring matter. for example anindigoid or thioindigoid colouring matter or a colouring mattercontaining a single anthraquinone nucleus, so as to leave uncolourcd thecotton or regenerated celulose. The latter may then, if desired. be dyedwith suitable colouring matters .herci'or. Alternatively the cellulosicportion oi the material may be coloured prior to the cellulose. acetatepart; for example the cellulosic portion may be dyed with a vat dyestuflin the presence of alkali salts of arcmatic hydroxy compounds asdescribed in U. S. Patent No. 1,716,720 so as to leave unstained the celulose acetate and the latter then dyed with a vat dyestufi' in the formof a dispersion of its free leuco compound.

The following examples show the best Way ligown to us of carrying theinvention into 0. 'ect:

Example I 200 grams of the brominated indigo known as Ciba blue G powder(Colour Index No. 1185) are pasted with 2.5 litres of the solution ofsodium salt of sulphonaphthalene ricinoleic acid prepared according toExample A of U. S. Patent No. 1.69%,413, and 4:0 to litres of Water atC. added with stirring. 200 grams of caustic soda are now added, and 350grams of sodium hydrosulphite sprinkled in with good stirring, andstirring continned for 5-10 minutes or till reduction is complete, afterwhich the liquor is filtered into a dyebath containing 500 litres ofsoft water at 50 C. to which 50 grams of hydrosulphite have previouslybeen added. The dyebath is now rendered slightly acid to litmus bycareful addition of approximately 3 litres of 10% acetic acid, wherebythe tree leuco compound is obtained as a very satisfactory dispersion.10 kilograms of cellulose acetate yarn in bank form are now entered, andthe temperature raised to 7580 C. in 1 1/ hour and held thereabouts fork to our.

The goods are now lifted, rinsed in soft water, hydro-extracted, andhung up to oxidize, after which they are given a light soaping in a 1gram per litre soap bath to which perborate may advantageously be added,rinsed, and dried or otherwise treated as req- Lusite.

Example 2 200 grams of the vat dyestufi known as Caledon jade green(Colour Index No. 1101) are pasted with 2.5 litres of a highly sulpho 1nated castor oil stable to dilute organic acids,

suitably diluted, and vatted with 200 grams of caustic soda and 350grams hydrosulphite as in Example 1. The clear solution is now added tothe dyebath previously set with hydrosulphite, acidified, and 10 kilosof cellulose acetate yarn in hank form entered and processed exact y asdetailed in that example. After oxidation, and soaping, the goods whichare now dyed a bright green, shade, are rinsed and dried or otherwisetreated as requisite.

In the same manner cellulose acetate yarns may be coloured in red shadesby means of Caledon red BN (Colour Index 1162), or in yellow shades bymeans of 2':5'-dichloro- 1 Q-anthraquinone thioxanthone.

Example 5 200 grams of the indophenol dyestuff prepared by oxidation ofp-aminodimethylaniline and alphanaphthol (Colour Index No. 831) arepasted with 1 litre of sulphite cellulose liquor, or an equivalentquantity of a suitable product of transformation, and 40 to 50 litres ofwater at 60 C. are added with stirring. 200 grams of caustic soda arenow added and 300 grams hydrosulphite sprinkled in with stirring, andstirring continued till vatting is complete, after which the liquor isfiltered into a suitable dyebath containing 500 litres of soft water at50 C. previously set with 50 grams of hydrosulphite. The dyebath is nowacidified by careful addition of approximately 3 litres of 10% aceticacid, and 10 kilograms of cellulose acetate woven fabric entered, afterwhich the temperature is raised to 7 5 to 80 C. in hour and heldthereabouts for hour. The goods are now lifted, rinsed, hydroextracted,and allowed to oxidize in the air, or in a bath containing 1 gram perlitre soap and 2 grams per litre sodium perborate till the colour isfully developed, after which they are lifted, rinsed, and dried orotherwise treated as requisite.

I Ewample 4 1 kilogram of a well ground 20% aqueous paste of the leucocompound of 1 benzoylaminol-oxy-anthraquinone is added to a solution of150 grams of gelatine dissolved in 10 litres of water rendered faintlyacidic with acetic acid. The whole is warmed to 80 C. and stirred toensure eflicient dispersion, and then diluted in a suitable machine to300 litres with warm soft water. 10 kilos of a woven fabric consistingof equal parts of wool and cellulose acetate previously well wetted out,are now entered, and dyeing carried out hour to 7580 C. and hour at 75C. or thereabouts. The goods are now lifted, rinsed, and oxidized bytreating for 5 minutes at 60 C. in a 300 litre bath containing 50 gramsbichromate of soda, and 250 ccs. 10% sulphuric acid.

The goods are now lifted, rinsed, soaped lightly, washed off well, anddried or otherwise treated as requisite. dyed in full shades of pink.

Ewample 5 To dye 10 kilos of a woven fabric consisting of equal parts ofcotton and cellulose acetate, the cotton green and the cellulose ace-The whole is heated to 95 C. with stirring,

and stirred till a good dispersion is achieved.

The whole is now diluted suitably with hotsoft water and added through afilter cloth to a dyebath containing 300 litres of soft water from whichdissolved oxygen has been Both fibres are Example 6 Cellulose acetatewoven fabric previously dyed with a violet dyestuif dischargeable withformosul, for example the dyestufi' obtained by coupling diazotized 3:5-dinitro-2- amino-anisole with alphanaphthylamine, is

. requisite.

' printed with a printing paste prepared as follows Grams Gum arabic 1:1 560 Ciba pink B 30 'Sodium sulpho-naphthalenericinoleate prepared asin U. S. Patent No.

1,694,413 50 Caustic so 30 Water 140 Hydrosulphite 40 The above areheated till vatted, cooled, and

a liquor consisting of a mixtue of Grams Formic acid 40% 90 Formosul 60added slowly with good stirring. The

amount of liquor added should be Just sufficient to neutralize or renderthe paste only faintly acid. I After printing the goods are dried,passed through a rapid ager or other suitable steaming device, and thenoxidized at 60C. for 5 minutes in a bath containing 2.5 grams per litrechrome and 5 grams per litre sulphuric acid. The goods are now rinsed,soaped well, washed off, and dried or otherwise treated as requisite.

What we claim and desire Letters Patent-is:-

' 1. Process for the coloration of textile and other materialscontaining organic derivatives of cellulose comprising applying theretofree leuco compounds of vat dyestuffs.

' 2. Process for the coloration of textile and other materialscontaining organic derivatives of cellulose comprising applying theretofree leuco compounds of vat dyestuffs in the form of aqueousdispersions.

3. Process for the coloration of textile and other materials containingorganic derivatives of cellulose comprising applying thereto free leucocompounds of vat dyestuffs in the form of aqueous dispersions having apH value between 3 and 9.

4. Process for the coloration of textile and other materials containingorganic derivatives of cellulose comprisin appl ing thereto free leucocompounds 0 vat yestufis in to secure by the form of aqueous dispersionshaving a slightly acid reaction.

' agent.

6. Process for the coloration of textile and other materials containingcellulose acetate comprising applying thereto free leuco compounds ofvat dyestuffs.

7. Process for the coloration of textile and other materials containingcelluloseacetate comprising applying thereto free leuco compounds of vatdyestufis in the form of aque- I ous dispersions.

8. Process for the coloration of textile and other materials containingcellulose acetate comprising applying thereto free leuco compounds ofvat dyestufi's in the form of aqueous dispersions having a pH valuebetween 3 and 9.

9. Process for the coloration of textile and other materials containingcellulose acetate comprising applying thereto free leuco compounds ofvat dyestufi's in the form of aqueous dispersions having a slightly acidreaction.

10. Process for the coloration of textile and other materials containingcellulose acetate comprising applying thereto a composition comprising afree leuco compound of a vat dyestuff and a dispersing agent.

11. Process for the coloration of textile and other materials containingorganic derivatives of cellulose comprising applying thereto free leucocompounds of indigoid vat dyestuds.

12. Process for the coloration of textile and other materials containingcellulose acetate comprising applying thereto free leuco compounds ofindigoid vat dyestuffs.

13. Process for the coloration of textile and other materials containingcellulose acetate comprising applying thereto a composition comprising afree leuco compound of an indigoid Vat dyestufi' and a dispersing agent.

14. Process for the coloration of textile and other materials containingorganic derivatives of cellulose comprising applying thereto .free leucocompounds of anthraquinone vat dyestufl's.

15. Process for the coloration of textile and other materials containingcellulose acetate comprising applying thereto free leuco compounds ofanthraquinone vat dyestuffs.

16. Process for the coloration of textile and other materials containingorganic derivatives of cellulose comprising applying thereto free leucocompounds of anthraquinone vat dyestufi's containing only oneanthraquinone residue.

17. Process for the coloration of textile and other materials containingcellulose acetate momma comprising ap lying thereto free leuco compoundsof ant raqulnone vat dyestufi's containing only one antraquinoneresidue.

18. Process for the coloration of textile and other materials containingcellulose acetate comprising applying thereto a composition comprising afree leuco compound of an anthraquinone vat dyestufl' containing onlyone anthraquinone residue and a dispersing agent.

19. Process for the coloration of textile and other materials containingcellulose acetate comprising applyin thereto free leuco compounds ofaminoant raquinones.

20. Process for the coloration of textile and other materials containingorganic derivatives of cellulose comprising applying thereto a.preparation made by vatting a vat dyestufi' in alkaline medium andadding in the presence of a dispersing agent at least sulficient acid toseparate free leuco compound of the dyestufi.

21. Process for the coloration of textile and other materials containingcellulose acetate comprising applying thereto a preparation made byvatting a vat dyestufi in alkaline medium and adding in the presence ofa dispersing agent at least sufiicient acid to separate free leucocompound of the dyestufi.

22. Process for the coloration of textile and other materials containingor anic derivatives of cellulose and animal fi res comprising applyingthereto free leuco compounds of vat dyestufis.

23. Process for the coloration of textile and other materials containingcellulose acetate and animal fibres comprising applying thereto freeleuco compounds of vat dyestufis.

In testimony whereof we have hereunto subscribed our names.

.. GEORGE HOLLAND ELLIS. HENRY CHARLES OLPIN. RALPH CHARLES STOREY.

, CERTIFICATE OF CORRECTION.

Patent No. 1,900,172. March 7, 1933.

GEORGE HOLLAND ELLIS, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,line 55, after "materials" insert the words "made of or containingcellulose acetate or other organic derivatives of cellulose"; and thatthe saidv Letters Patent should be read with this correction thereinthat the same may conform to the record of the case in the PatentOffice.

Signed and sealed this 9th day of May, A. D. 1933.

M. J. Moore.

(Seal) Acting Gommisioner of Patents.

